JP2015142706A - Resin composition for golf ball and golf ball - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for golf balls which has excellent flexibility, fluidity, and resilience, and golf balls using the resin composition.SOLUTION: A resin composition for golf balls includes a polymer that contains a diene polymer moiety and a carboxylic acid-based moiety, and in which carboxyl groups derived from the carboxylic acid-based moiety are neutralized. In the resin composition for golf balls, the polymer is obtained by neutralizing the carboxyl groups derived from an unsaturated carboxylic acid compound contained in a reaction product of the C2-C18 unsaturated carboxylic acid compound and the dien polymer having an α,β-unsaturated carbonyl group at each end.

Description

The present invention relates to a resin composition for golf balls and a golf ball using the same.

Golf ball materials are generally required to have good shot feel, flight distance, and productivity, and studies have been made on improving flexibility, resilience, and fluidity related to these performances.

As such materials, ethylene / acrylic acid copolymer ionomers, butadiene rubber and zinc acrylate composites, etc. have been proposed. Although ionomers have excellent fluidity and high resilience, they are poor in flexibility and composites. Has excellent flexibility and high resilience, but has a problem of poor fluidity.

An object of the present invention is to solve the above-mentioned problems and to provide a golf ball resin composition excellent in flexibility, fluidity and resilience, and a golf ball using the same.

The present invention relates to a golf ball resin composition comprising a polymer having a diene polymer moiety and a carboxylic acid moiety and having a carboxyl group derived from the carboxylic acid moiety neutralized.

The polymer is derived from the unsaturated carboxylic acid compound in the reaction product of a diene polymer having α, β-unsaturated carbonyl groups at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. It is preferably obtained by neutralizing a carboxyl group.

The diene polymer is a diene polymer having an acryloyl group, the unsaturated carboxylic acid compound is acrylic acid and / or a derivative thereof, or the diene polymer is a diene polymer having a methacryloyl group, The saturated carboxylic acid compound is preferably methacrylic acid and / or a derivative thereof.

The polymer is an unsaturated carboxylic acid compound in a reaction product of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. It is preferable that it is obtained by neutralizing the carboxyl group derived from it.

The diene polymer is at least one selected from the group consisting of both ends of a diene polymer and primary to tertiary chloroalkane structures, primary to tertiary bromoalkane structures, and primary to tertiary iodoalkane structures. Are preferably bonded via at least one selected from the group consisting of an ether bond, a thioether bond, an ester bond, a thioester bond, a silyl ester bond and a urethane bond.

The diene polymer preferably includes a 1,4-cis structure.

The unsaturated carboxylic acid compound is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof.

The content of the unsaturated carboxylic acid compound is preferably 8 to 50% by mass.

The neutralization degree of the carboxyl group is preferably 20 to 300%.

The product of the content of the unsaturated carboxylic acid compound and the degree of neutralization of the carboxyl group is preferably 160 to 4500.

The polymer is obtained by neutralizing a (anhydrous) dicarboxyl group of a diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more. It is preferable.

The content of the (anhydrous) dicarboxylic acid is preferably 2 to 30% by mass.

The neutralization degree of the (anhydrous) dicarboxyl group is preferably 20 to 300%.

The product of the content of the (anhydrous) dicarboxylic acid and the degree of neutralization of the (anhydrous) dicarboxyl group is preferably 80 to 4500.

The polymer is preferably obtained by neutralizing a carboxyl group and (anhydrous) dicarboxyl group in a reaction product of a diene polymer grafted with (anhydrous) dicarboxylic acid and a diol compound.

The diene polymer preferably includes a 1,4-cis structure.

The diol compound has 2 to 20 carbon atoms having 2 hydroxyl groups, 2 hydroxyl groups, 2 to 20 carbon atoms having at least one ether bond, 2 hydroxyl groups, carboxyl It is preferably at least one selected from the group consisting of a hydrocarbon having 2 to 20 carbon atoms having 1 to 3 groups and a polymer hydrocarbon having 2 hydroxyl groups.

The content of carboxyl groups and (anhydrous) dicarboxyl groups in the reaction product is preferably 4 to 50% by mass.

It is preferable that the neutralization degree of the carboxyl group and (anhydrous) dicarboxyl group in the polymer is 20 to 300%.

The (anhydrous) dicarboxylic acid is at least one selected from the group consisting of (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, and (anhydrous) adipic acid, and the diene polymer. It is preferable that it is directly bonded to the main chain and / or the terminal.

The carboxyl group is preferably neutralized by at least one metal ion selected from the group consisting of Na ⁺ , Mg ²⁺ , Ca ²⁺ and Zn ²⁺ .

The present invention also provides (A) a diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more, (B) an olefin and an α having 3 to 8 carbon atoms. , Β-unsaturated carboxylic acid binary copolymer (b-1), metal ion neutralized product of olefin and binary copolymer of C 3-8 α, β-unsaturated carboxylic acid ( b-2), a terpolymer (b-3) of an olefin, an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α, β-unsaturated carboxylic acid ester, and the olefin and the carbon number At least one selected from the group consisting of metal ion neutralized products (b-4) of terpolymers of 3 to 8 α, β-unsaturated carboxylic acid and α, β-unsaturated carboxylic acid ester The present invention relates to a golf ball resin composition containing:

The (anhydrous) dicarboxylic acid in the component (A) is at least one selected from the group consisting of (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, and (anhydrous) adipic acid, and It is preferable that the diene polymer is directly bonded to the main chain and / or terminal of the diene polymer.

The diene polymer as the component (A) preferably has a content of the (anhydrous) dicarboxylic acid of 1% by mass or more.

It is preferable that the compounding quantity of the said (A) component is 1-70 mass parts with respect to 100 mass parts of said (B) component.

The α, β-unsaturated carboxylic acid in the component (B) is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, and (anhydrous) maleic acid.

The content of α, β-unsaturated carboxylic acid in the component (B) is preferably 4 to 50% by mass.

The metal ion neutralized product in the component (B) preferably has a neutralization degree of 50 to 500%.

The neutralized metal ion in the component (B) preferably has a product of the content of α, β-unsaturated carboxylic acid and the degree of neutralization of 750 to 5500.

(C) It is preferable to further contain at least one metal ion selected from the group consisting of Na ⁺ , Mg ²⁺ , Ca ²⁺ , and Zn ²⁺ .

The present invention also relates to a golf ball produced using the golf ball resin composition.

According to the present invention, since it is a resin composition for a golf ball having a diene polymer moiety and a carboxylic acid moiety, and containing a polymer in which a carboxyl group derived from the carboxylic acid moiety is neutralized, excellent flexibility , Fluidity, and resilience can be imparted.

[First Golf Ball Resin Composition]
The resin composition for a golf ball of the first aspect of the present invention contains a polymer having a diene polymer portion and a carboxylic acid-based portion, and a carboxyl group derived from the carboxylic acid-based portion is neutralized.

Such a polymer, for example, a polymer moiety derived from a diene monomer such as butadiene (diene polymer moiety) and a derivative such as an unsaturated carboxylic acid, (anhydrous) dicarboxylic acid, or an ester thereof can generate a carboxyl group. Good flexibility, fluidity, and resilience can be obtained by using a polymer having a site derived from a carboxylic acid compound (a carboxylic acid site) and having the carboxyl group neutralized.

The resin composition for golf balls of the first aspect of the present invention is not particularly limited as long as it contains the polymer, and as a preferred form, a diene polymer having α, β-unsaturated carbonyl groups at both ends and the number of carbon atoms A golf ball resin composition containing a polymer obtained by neutralizing a carboxyl group derived from an unsaturated carboxylic acid compound in a reaction product with 2-18 unsaturated carboxylic acid compounds (hereinafter referred to as a first compound). In a reaction product of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. Golf ball resin composition (hereinafter referred to as first golf ball resin composition 2) containing a polymer obtained by neutralizing the carboxyl group derived from the unsaturated carboxylic acid compound, (anhydrous) dica Golf ball resin composition comprising a polymer obtained by neutralizing a (anhydrous) dicarboxyl group of a diene polymer grafted with rubonic acid and having a 1,4-cis structure content of 41% by mass or more ( Hereinafter, the first golf ball resin composition 3), and the reaction product of the diene polymer grafted with (anhydrous) dicarboxylic acid and the diol compound, neutralize the carboxyl group and (anhydrous) dicarboxyl group. A golf ball resin composition containing the polymer obtained in this manner (hereinafter referred to as the first golf ball resin composition 4).

(First Golf Ball Resin Composition 1)
The first golf ball resin composition 1 includes a reaction product of a diene polymer having α, β-unsaturated carbonyl groups at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. It includes a polymer obtained by neutralizing a carboxyl group derived from an unsaturated carboxylic acid compound.

In addition, “a carboxyl group derived from the unsaturated carboxylic acid compound in the reaction product of a diene polymer having α, β-unsaturated carbonyl groups at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms” When the unsaturated carboxylic acid compound is an unsaturated carboxylic acid, the golf ball resin composition obtained by neutralizing the carboxylic acid group is a carboxyl group present in the reaction product of a diene polymer and an unsaturated carboxylic acid. It is obtained by neutralizing (carboxyl group in unsaturated carboxylic acid unit). Further, when the unsaturated carboxylic acid compound is an unsaturated carboxylic acid derivative such as an unsaturated carboxylic acid ester, from the unsaturated carboxylic acid derivative unit present in the reaction product of the diene polymer and the unsaturated carboxylic acid derivative. In the case of the produced carboxyl group, for example, t-butyl acrylate, it is obtained by neutralizing the carboxyl group produced by eliminating the t-butyl group from the t-butyl acrylate unit in the reaction product. is there.

The diene polymer constituting the skeleton of the diene polymer having α, β-unsaturated carbonyl groups at both ends is a diene polymer. A diene is a compound having two double bonds in the molecule, and is preferably a conjugated diene. Examples of dienes include 1,2-propadiene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, and 1,2. -Pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene and the like can be mentioned. Of these, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene (isoprene) are preferable.

The diene polymer constituting the skeleton of the diene polymer having α, β-unsaturated carbonyl groups at both ends has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. .
In addition, in this invention, a number average molecular weight can be measured by standard polystyrene conversion based on the measured value by a gel permeation chromatography (GPC).

The diene polymer constituting the skeleton preferably includes a 1,4-cis structure, and the cis content of the diene polymer (content of 1,4-cis structure) is more preferably 10% by mass or more. 20% by mass or more is more preferable. By setting it to 10% by mass or more, good resilience can be obtained.

The α, β-unsaturated carbonyl group is not particularly limited, and examples thereof include a (meth) acryloyl group and an α, β-unsaturated amide group. Of these, a (meth) acryloyl group is preferable from the viewpoint of flexibility, fluidity, and resilience. The α, β-unsaturated carbonyl groups at both ends may be either the same group or different groups, but the same group is preferred.

As the α, β-unsaturated carbonyl group-containing compound capable of introducing an α, β-unsaturated carbonyl group at both ends of the diene polymer, a mono- or polyfunctional compound can be used, specifically, t-butyl. (Meth) acrylate, 2-hydroxy-1,3-dimethacryloxypropane, methylenebisacrylamide, (meth) acrylamide, (meth) acrylic acid, anhydrous (meth) acrylic acid, (meth) acrylic acid chloride, (meth) Acrylic acid bromide, vinyl imidazole ketone, 1- (1-methylvinyl) imidazole ketone, 2-isocyanate ethyl acrylate and the like can be mentioned. Of these, (meth) acrylic acid chloride and (meth) acrylic acid bromide are preferable from the viewpoint of flexibility, fluidity, and resilience.

A diene polymer having an α, β-unsaturated carbonyl group at both ends can be prepared by a conventionally known production method, for example, a functional group having reactivity with an α, β-unsaturated carbonyl group-containing compound at both ends. It can be obtained by a method of reacting the diene polymer having the compound with the compound. Specifically, by reacting a diene polymer having hydroxyl groups at both ends with an α, β-unsaturated carbonyl group-containing compound such as (meth) acrylic acid chloride or (meth) acrylic acid bromide by a known method. Prepared.

In the polymer in the golf ball resin composition 1, an unsaturated carboxylic acid compound having 2 to 18 carbon atoms is used. In the present specification, the term “unsaturated carboxylic acid compound” means at least in the molecule. It is a compound having one double bond and a carboxyl group or a derivative group thereof (such as a carboxylic acid ester group). The number of carbon atoms of the unsaturated carboxylic acid compound is preferably 3-8.

Examples of unsaturated carboxylic acid compounds include unsaturated carboxylic acids, derivatives thereof (unsaturated carboxylic acid esters, etc.), and specifically, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid (trans -2-butenoic acid), isocrotonic acid (cis-2-butenoic acid), sorbic acid, citraconic acid, mesaconic acid; and their derivatives (esters, etc.). Of these, acrylic acid, methacrylic acid, and derivatives thereof (esters such as t-butyl acrylate) are preferable from the viewpoints of flexibility, fluidity, and resilience.

In particular, from the viewpoint that the reactivity between the diene polymer and the unsaturated carboxylic acid compound is increased, and flexibility, fluidity, and resilience are remarkably improved, (1) having an acryloyl group as the diene polymer A resin composition obtained by using a diene polymer and using acrylic acid and / or a derivative thereof (acrylic ester, etc.) as the unsaturated carboxylic acid compound, (2) a methacryloyl group as the diene polymer The resin composition obtained by using the diene polymer which has and using methacrylic acid and / or its derivative (methacrylic ester etc.) as said unsaturated carboxylic acid type compound is preferable.

The polymer in the golf ball resin composition 1 is prepared by reacting (copolymerizing) the diene polymer and the unsaturated carboxylic acid compound using a known method, and reacting the carboxyl group in the obtained reaction product. It is obtained by neutralizing a carboxyl group derived from an unsaturated carboxylic acid compound generated from the product.

For example, a diene polymer such as polybutadiene having an α, β-unsaturated carbonyl group such as an acrylate group at both ends and t-butyl acrylate are mixed at a predetermined ratio, and the mixture is coexisted in the presence of a polymerization initiator, a catalyst, and the like. By polymerizing and further removing the t-butyl group of the protective group, a butadiene / acrylic acid copolymer having a predetermined carboxyl group is obtained, and then neutralizing the carboxyl group with an inorganic metal compound, The polymer can be prepared. As a polymerization method, a living radical polymerization method is preferable, and among them, an atom transfer radical polymerization method (ATRP) is particularly preferable. In addition, neutralization of the carboxyl group is specifically performed by melting the reaction product or a product obtained by generating a carboxyl group derived from an unsaturated carboxylic acid compound from the reaction product, and placing the product in the melt. It can be carried out by adding a certain amount of inorganic metal compound and kneading.

As an inorganic compound, the compound which can neutralize a carboxyl group is used, without being specifically limited, For example, the compound containing Na, Mg, Ca, Zn etc. is mentioned. Especially, the compound containing Na, Mg, Ca, and Zn is preferable, and in this case, the metal ions of Na ⁺ , Mg ²⁺ , Ca ²⁺ , and Zn ²⁺ are neutralized.

In 100% by mass of the polymer, the content of the unsaturated carboxylic acid compound is preferably 8% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The content is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. By adjusting within the above range, good resilience can be obtained.

In the polymer, the content ratio of the diene polymer and the unsaturated carboxylic acid compound (diene polymer / unsaturated carboxylic acid compound (mass ratio)) is, from the viewpoint of the effect of the present invention,
1/1 to 1 / 0.087 is preferable, and 1 / 0.429 to 1 / 0.111 is more preferable.

The neutralization degree of the carboxyl group of the polymer is preferably 20% or more, more preferably 50% or more, and still more preferably 80% or more. Moreover, 300% or less is preferable, 200% or less is more preferable, and 100% or less is still more preferable. By adjusting within the above range, good resilience can be obtained.
In this specification, the degree of neutralization of carboxyl groups is the ratio of the number of moles of neutralized carboxyl groups to the total number of moles of carboxyl groups contained in the polymer.

The degree of neutralization is calculated from the amount of raw material charged. For example, the degree of neutralization in the polymer determined by melting the polymer in tetrahydrofuran with heat and titrating with a prescribed concentration of potassium hydroxide in a heated state. From the number of moles of the unneutralized carboxyl group ([COOH]) of the saturated carboxylic acid and the number of moles of the neutralized carboxyl group ([COOM]) calculated by metal analysis, it can also be calculated by the following formula.
Degree of neutralization (mol%) = [COOM] / ([COOH] + [COOM]) × 100

As the metal analysis, for example, a monovalent metal such as sodium can be performed by a polarized Zeeman atomic absorption spectrophotometer model 180-80 manufactured by Hitachi, Ltd., and a divalent metal such as zinc can be analyzed by, for example, Seiko. This can be carried out using a sequential type ICP emission spectrometer SPS1100 manufactured by Denki Kogyo.

The product (mass% ·%) of the content of the unsaturated carboxylic acid compound in 100% by mass of the polymer and the neutralization degree of the carboxyl group is preferably 160 to 4500, more preferably 300 to 3000, 1200-1500 are more preferable. The effect of this invention can fully be exhibited as it exists in the said range.

(First Golf Ball Resin Composition 2)
The first golf ball resin composition 2 includes a reaction product of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. And a polymer obtained by neutralizing a carboxyl group derived from the unsaturated carboxylic acid compound.

"From the unsaturated carboxylic acid compound in the reaction product of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms" When the unsaturated carboxylic acid compound is an unsaturated carboxylic acid, it is present in the reaction product of a diene polymer and an unsaturated carboxylic acid. It is obtained by neutralizing the carboxyl group (carboxyl group in the unsaturated carboxylic acid unit). Further, when the unsaturated carboxylic acid compound is an unsaturated carboxylic acid derivative such as an unsaturated carboxylic acid ester, from the unsaturated carboxylic acid derivative unit present in the reaction product of the diene polymer and the unsaturated carboxylic acid derivative. In the case of the produced carboxyl group, for example, t-butyl acrylate, it is obtained by neutralizing the carboxyl group produced by eliminating the t-butyl group from the t-butyl acrylate unit in the reaction product. is there.

The diene polymer constituting the skeleton of the diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends is a diene polymer and is the same as described above.

The diene polymer constituting the skeleton of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. It is.

The diene polymer constituting the skeleton preferably includes a 1,4-cis structure, and the cis content of the diene polymer (content of 1,4-cis structure) is more preferably 10% by mass or more. 20% by mass or more is more preferable. By setting it to 10% by mass or more, good resilience can be obtained.

The halogenated alkane structure having 1 to 18 carbon atoms is not particularly limited, and examples thereof include primary to tertiary chloroalkane structures, primary to tertiary bromoalkane structures, and primary to tertiary iodoalkane structures. Among these, a tertiary bromoalkane structure is preferable from the viewpoint of flexibility, fluidity, and resilience. The halogenated alkane structures at both ends may be either the same structure or different structures, but the same structure is preferred.

Examples of the halogenated alkane structure-containing compound capable of introducing a C1-C18 halogenated alkane structure at both ends of the diene polymer include bromoisobutyric acid bromide, bromoisobutyric acid, bromoisobutyric anhydride, bromoisobutyric acid imidazole, 1-bromo- Examples include 3-chloropropane, 2-chloro-2-methylethyl isocyanate, chloro (2-bromo-2-methylpropyl) dimethylsilane, and the like. Of these, bromoisobutyric acid bromide is preferable in terms of flexibility, fluidity, and resilience.

A diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends can be prepared by a conventionally known production method. For example, a diene having functional groups at both ends having reactivity with a halogenated alkane structure-containing compound. It can be obtained by a method of reacting a polymer with the compound. Specifically, it is prepared by reacting a diene polymer having a hydroxyl group at both ends with a halogenated alkane structure-containing compound such as bromoisobutyric acid bromide by a known method.

The diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends prepared as described above includes the both ends of the diene polymer, a primary to tertiary chloroalkane structure, and a primary to tertiary bromoalkane. And at least one selected from the group consisting of a structure and a primary to tertiary iodoalkane structure is at least one selected from the group consisting of an ether bond, a thioether bond, an ester bond, a thioester bond, a silyl ester bond and a urethane bond It is preferable that they are bonded via a seed.

For example, by reacting a diene polymer having hydroxyl groups at both ends with bromoisobutyric acid bromide, bromoisobutyric acid, bromoisobutyric anhydride, or imidazole bromoisobutyrate by a known method, a tertiary bromoalkane structure via an ester bond Can be combined. In addition to bromoisobutyric acid bromide, bromoisobutyric acid, bromoisobutyric anhydride, bromoisobutyric acid imidazole, chloroacetic anhydride, chloroacetic anhydride, chloroacetic acid chloride, chloroacetic acid imidazole, bromoacetic acid can be used to link halogenated alkane structures via ester bonds. Bromoacetic anhydride, bromoacetic acid bromide, bromoacetic acid imidazole, iodoacetic acid, anhydrous iodoacetic acid, iodoacetic acid iodide, iodoacetic acid imidazole, chloro-1-propanoic acid, chloro-1-propanoic acid anhydride, chloro-1-propanoic acid chloride Chloro-1-propanoic acid imidazole, chloro-2-propanoic acid, chloro-2-propanoic anhydride, chloro-2-propanoic acid chloride, chloro-2-propanoic acid imidazole, bromo-1-propanoic acid, bromo- 1-propanoic acid, bromine -1-propanoic acid bromide, bromo-1-propanoic acid imidazole, bromo-2-propanoic acid, bromo-2-propanoic anhydride, bromo-2-propanoic acid bromide, bromo-2-propanoic acid imidazole, iodo-1- Propanoic acid, anhydrous iodo-1-propanoic acid, iodo-1-propanoic acid iodide, iodo-1-propanoic acid imidazole, iodo-2-propanoic acid, anhydrous iodo-2-propanoic acid, iodo-2-propanoic acid iodide iodo- You may make 2-propanoic acid imidazole react.

Further, by reacting 1-bromo-3-chloropropane with a diene polymer having hydroxyl groups at both ends by a known method, a primary chloroalkane structure can be bonded through an ether bond. In order to bond a halogenated alkane structure via an ether bond, in addition to 1-bromo-3-chloropropane, bromochloroethane, bromoiodoethane, 1-bromo-3-iodopropane, 1-bromo-4-chlorobutane, 1-bromo-4-iodobutane, 1-bromo-3-chlorobutane, 3-bromo-1-iodobutane and the like may be reacted.

Further, a secondary chloroalkane structure can be bonded via a urethane bond by reacting 2-chloro-2-methylethyl isocyanate with a diene polymer having hydroxyl groups at both ends by a known method. In order to bond a halogenated alkane structure via a urethane bond, in addition to 2-chloro-2-methylethyl isocyanate, 2-chloro-2,2-dimethylethyl isocyanate, 2-bromo-2,2-dimethylethyl Isocyanate, 2-bromo-2-methylethyl isocyanate, 2-chloroethyl isocyanate, 2-bromoethyl isocyanate and the like may be reacted.

A tertiary bromoalkane structure is bonded via a silyl ester bond by reacting a diene polymer having hydroxyl groups at both ends with chloro (2-bromo-2-methylpropyl) dimethylsilane by a known method. Can be made. In order to bond a halogenated alkane structure via a silyl ester bond, in addition to chloro (2-bromo-2-methylpropyl) dimethylsilane, chloro (2-chloro-2-methylpropyl) dimethylsilane, chloro (2 -Chloropropyl) dimethylsilane, chloro (2-bromopropyl) dimethylsilane, chloro (2-chloroethyl) dimethylsilane, chloro (2-bromoethyl) dimethylsilane and the like may be reacted.

In the polymer in the golf ball resin composition 2, an unsaturated carboxylic acid compound having 2 to 18 carbon atoms is used. As the unsaturated carboxylic acid compound, for example, the same compounds as described above can be preferably used.

In particular, from the viewpoint that the reactivity between the diene polymer and the unsaturated carboxylic acid compound is increased, and flexibility, fluidity, and resilience are remarkably improved, (1) the diene polymer is esterified at both ends. A resin composition obtained by using a diene polymer having a tertiary bromopropane structure via a bond, and using acrylic acid and / or a derivative thereof (acrylic ester, etc.) as the unsaturated carboxylic acid compound (2) A diene polymer having a tertiary bromopropane structure via ester bonds at both ends is used as the diene polymer, and methacrylic acid and / or a derivative thereof (methacrylic acid) is used as the unsaturated carboxylic acid compound. Resin compositions obtained using acid esters and the like are preferred.

The polymer in the golf ball resin composition 2 is prepared by reacting (copolymerizing) the diene polymer and the unsaturated carboxylic acid compound using a known method, and reacting with the carboxyl group in the obtained reaction product. It is obtained by neutralizing a carboxyl group derived from an unsaturated carboxylic acid compound generated from the product.

For example, a diene polymer such as polybutadiene having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and t-butyl acrylate are mixed in a predetermined ratio and copolymerized in the presence of a polymerization initiator, a catalyst, or the like. Further, by removing the t-butyl group of the protective group, a butadiene / acrylic acid copolymer having a predetermined carboxyl group is obtained, and then the polymer is obtained by neutralizing the carboxyl group with an inorganic metal compound. Can be prepared. As a polymerization method, a living radical polymerization method is preferable, and among them, an atom transfer radical polymerization method (ATRP) is particularly preferable. In addition, neutralization of the carboxyl group is specifically performed by melting the reaction product or a product obtained by generating a carboxyl group derived from an unsaturated carboxylic acid compound from the reaction product, and placing the product in the melt. It can be carried out by adding a certain amount of inorganic metal compound and kneading. In addition, as an inorganic metal compound, the thing similar to the above can be used conveniently, for example.

In addition, after obtaining a butadiene / acrylic acid copolymer having a predetermined carboxyl group by the above method, each copolymer is condensed using a condensing agent capable of condensing each copolymer to increase the molecular weight. The polymer may be prepared by neutralizing with an inorganic metal compound.

The structure of the polymer is not particularly limited, and a structure in which a unit of a diene polymer and an unsaturated carboxylic acid compound are randomly bonded, a unit of a polymer of an unsaturated carboxylic acid compound-a unit of a diene polymer- Examples include a triblock copolymer structure formed from a polymer unit of an unsaturated carboxylic acid compound, a structure obtained by condensing polymers of the triblock copolymer structure, and the like.

In 100% by mass of the polymer, the content of the unsaturated carboxylic acid compound is preferably 8% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The content is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. By adjusting within the above range, good resilience can be obtained.

In the polymer, the content ratio of the diene polymer and the unsaturated carboxylic acid compound (diene polymer / unsaturated carboxylic acid compound (mass ratio)) is, from the viewpoint of the effect of the present invention,
1/1 to 1 / 0.087 is preferable, and 1 / 0.429 to 1 / 0.111 is more preferable.

The neutralization degree of the carboxyl group of the polymer is preferably 20% or more, more preferably 50% or more, and still more preferably 80% or more. Moreover, 300% or less is preferable, 200% or less is more preferable, and 100% or less is still more preferable. By adjusting within the above range, good resilience can be obtained.

The product (mass% ·%) of the content of the unsaturated carboxylic acid compound in 100% by mass of the polymer and the neutralization degree of the carboxyl group is preferably 160 to 4500, more preferably 300 to 3000, 1200-1500 are more preferable. The effect of this invention can fully be exhibited as it exists in the said range.

(First Golf Ball Resin Composition 3)
The first golf ball resin composition 3 is an (anhydrous) dicarboxyl of a diene polymer in which (anhydrous) dicarboxylic acid is grafted (added) and the content of 1,4-cis structure is 41% by mass or more. Includes polymers obtained by neutralizing groups. Here, the location of the diene polymer to which (anhydrous) dicarboxylic acid is grafted (added) is not particularly limited, and the main chain (polymer chain), terminal (end of polymer chain), side chain (branched from polymer chain) Any portion of the polymer such as a chain) may be used.

The diene polymer constituting the skeleton of the diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more is a diene polymer and is the same as described above. is there.

The diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. belongs to.

The diene polymer constituting the skeleton contains a 1,4-cis structure, and the cis content of the diene polymer (content of 1,4-cis structure) is 41% by mass or more, Preferably it is 60 mass% or more. By setting the content to 41% by mass or more, good resilience can be obtained.

The (anhydrous) dicarboxylic acid is not particularly limited, and known dicarboxylic anhydrides and dicarboxylic acids can be used. For example, (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, (anhydrous) adipic acid, etc. Can be mentioned. Of these, maleic anhydride is preferable from the viewpoints of flexibility, fluidity, and resilience.

The diene polymer includes at least one (anhydrous) dicarboxylic acid selected from the group consisting of (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, and (anhydrous) adipic acid. Those directly bonded to the main chain and / or terminal of the polymer are preferred. The (anhydrous) dicarboxyl group bonded to the main chain or terminal may be either the same group or a different group, but the same group is preferred.

The diene polymer grafted with (anhydrous) dicarboxylic acid can be prepared by a conventionally known production method. For example, a diene polymer having a 1,4-cis structure is added to (anhydrous) dicarboxylic acid such as (anhydrous) maleic acid. Can be obtained by a known method such as graft addition.

In particular, it is preferable to use a diene polymer in which maleic anhydride is directly bonded to the main chain (polymer chain) from the viewpoint of significantly improving flexibility, fluidity, and resilience.

The golf ball resin composition 3 is obtained by grafting (anhydrous) dicarboxylic acid onto a diene polymer having a predetermined 1,4-cis structure amount using a known method, and (anhydrous) dicarboxylic acid in the resulting adduct. It is obtained by neutralizing the carboxyl group.

For example, a diene polymer having a 1,4-cis structure is dissolved in an organic solvent, a predetermined amount of (anhydrous) dicarboxylic acid such as (anhydrous) maleic acid is added thereto, and an organic peroxide or a polymerization inhibitor is present. A diene polymer having (anhydrous) dicarboxyl group is obtained by heating reaction under the following conditions, and then a resin composition can be prepared by neutralizing the (anhydrous) dicarboxyl group with an inorganic metal compound. . The neutralization of the (anhydrous) dicarboxyl group is specifically performed by melting the diene polymer having the (anhydrous) dicarboxyl group, adding a predetermined amount of an inorganic metal compound to the melt, and kneading. Can be implemented. At this time, a small amount of water may be added to promote the neutralization reaction. In addition, as an inorganic metal compound, the thing similar to the above can be used conveniently, for example.
Thus, (anhydrous) dicarboxylic acid is grafted, and the (anhydrous) dicarboxyl group of the diene polymer having a 1,4-cis structure content of 41% by mass or more is Na ⁺ , Mg ²⁺ , Ca ^2+, and it is neutralized by at least one metal ion selected from the group consisting of Zn ²⁺ is also one of the preferred embodiments of the present invention.

In 100% by mass of the polymer, the content of the (anhydrous) dicarboxylic acid is preferably 2% by mass or more, and more preferably 4% by mass or more. The content is preferably 30% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. By adjusting within the above range, good resilience can be obtained.

In the polymer, the content ratio of the diene polymer and the (anhydrous) dicarboxylic acid (diene polymer / (anhydrous) dicarboxylic acid (mass ratio)) is 1 / 0.041 to 1 from the viewpoint of the effect of the present invention. /0.176 is preferable, and 1 / 0.041 to 1 / 0.111 is more preferable.

The degree of neutralization of the (anhydrous) dicarboxyl group of the polymer is preferably 20% or more, more preferably 50% or more, and still more preferably 80% or more. Moreover, 300% or less is preferable, 200% or less is more preferable, and 100% or less is still more preferable. By adjusting within the above range, good resilience can be obtained.
The degree of neutralization of the (anhydrous) dicarboxyl group is the ratio of the number of moles of neutralized (anhydrous) dicarboxyl group to the total number of moles of (anhydrous) dicarboxyl group contained in the polymer.

The degree of neutralization is calculated from the amount of raw material charged. For example, the polymer is melted in tetrahydrofuran when heated and titrated with a prescribed concentration of potassium hydroxide in a heated state. From the number of moles of neutralized (anhydrous) dicarboxyl group ([COOCO] or [(COOH) ₂ ]) and the number of moles of neutralized (anhydrous) dicarboxyl group ([(COOM) ₂ ]) calculated by metal analysis It is also possible to calculate by the following formula.
Degree of neutralization (mol%) = [(COOM) ₂ ] / ([COOCO] + [(COOH) ₂ ] + [(COOM) ₂ ]) × 100
The metal analysis can be performed by the same method as described above, for example.

The product (mass% ·%) of the content of the (anhydrous) dicarboxylic acid in 100% by mass of the polymer and the degree of neutralization of the (anhydrous) dicarboxyl group is preferably 80 to 4500, and 200 to 3000. More preferably, 400-1500 is still more preferable. The effect of this invention can fully be exhibited as it exists in the said range.

(First Golf Ball Resin Composition 4)
The first golf ball resin composition 4 includes a reaction product of a diene polymer grafted (added) with (anhydrous) dicarboxylic acid (hereinafter also referred to as a grafted diene polymer) and a diol compound. Polymers obtained by neutralizing carboxyl groups and (anhydrous) dicarboxyl groups are included. Here, the location of the diene polymer to which (anhydrous) dicarboxylic acid is grafted (added) is not particularly limited, and the main chain (polymer chain), terminal (end of polymer chain), side chain (branched from polymer chain) Any portion of the polymer such as a chain) may be used.

The diene polymer constituting the skeleton of the diene polymer grafted with (anhydrous) dicarboxylic acid is a diene polymer and is the same as described above.

The diene polymer grafted with (anhydrous) dicarboxylic acid has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000.

Further, the diene polymer constituting the skeleton preferably includes a 1,4-cis structure, and the cis content (content of 1,4-cis structure) of the diene polymer is more preferably 41% by mass or more. 60 mass% or more is more preferable. By setting the content to 41% by mass or more, better resilience can be obtained.

The (anhydrous) dicarboxylic acid is not particularly limited, and known dicarboxylic anhydrides and dicarboxylic acids can be used. For example, (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, (anhydrous) adipic acid, etc. Can be mentioned. Of these, maleic anhydride is preferable from the viewpoints of flexibility, fluidity, and resilience.

The diene polymer includes at least one (anhydrous) dicarboxylic acid selected from the group consisting of (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, and (anhydrous) adipic acid. Those directly bonded to the main chain and / or terminal of the polymer are preferred. The (anhydrous) dicarboxyl group bonded to the main chain or terminal may be either the same group or a different group, but the same group is preferred.

The diene polymer grafted with (anhydrous) dicarboxylic acid can be prepared by a conventionally known production method as described above. For example, a diene polymer having a 1,4-cis structure can be converted into (anhydrous) maleic acid ( Anhydrous) dicarboxylic acid can be obtained by graft addition by a known method.

In particular, it is preferable to use a diene polymer in which maleic anhydride is directly bonded to the main chain (polymer chain) from the viewpoint of significantly improving flexibility, fluidity, and resilience.

In the polymer in the golf ball resin composition 4, a diol compound is used. The diol compound is not particularly limited as long as it is a compound having two hydroxyl groups in one molecule, but from the viewpoint of ensuring good fluidity of the finally obtained golf ball resin composition, 2 to 20 hydrocarbons having 2 carbon atoms, 2 hydroxyl groups, 2 to 20 carbon atoms hydrocarbons having at least one ether bond, 2 hydroxyl groups, and 1 to 3 carboxyl groups It is preferably at least one selected from the group consisting of hydrocarbons having 2 to 20 carbon atoms and polymer hydrocarbons having 2 hydroxyl groups, and hydrocarbons having 2 to 20 carbon atoms having 2 hydroxyl groups A hydrocarbon having 2 to 20 carbon atoms having two hydroxyl groups and at least one ether bond, and a hydrocarbon having 2 to 20 carbon atoms having two hydroxyl groups and 1 to 3 carboxyl groups More preferably, it is at least one selected from the group consisting of 2 to 20 carbon atoms having 2 hydroxyl groups, and 2 carbon atoms having 2 hydroxyl groups and 1 to 3 carboxyl groups. More preferably, it is at least one selected from the group consisting of ˜20 hydrocarbons. Here, the location where the diol compound has a hydroxyl group is not particularly limited, and any portion of hydrocarbon such as a terminal (end of hydrocarbon chain), a side chain (chain branched from the hydrocarbon chain) or the like may be used.

The hydrocarbon having 2 hydroxyl groups and having 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 8, more preferably 4 to 6) may be a saturated hydrocarbon or an unsaturated hydrocarbon. It may be. Further, it may be a linear or branched chain or may be cyclic (however, in the case of a cyclic hydrocarbon, it is a hydrocarbon having 3 to 20 carbon atoms). The cyclic hydrocarbon includes aromatic hydrocarbons (however, in the case of aromatic hydrocarbons, the number of carbon atoms is 6 to 20). Specific examples of the hydrocarbon having 2 to 20 carbon atoms having 2 hydroxyl groups include saturated hydroxyl groups having 2 hydroxyl groups such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, decanediol, and propylene glycol. Chain hydrocarbons; unsaturated chain hydrocarbons having two hydroxyl groups such as 2-pentene-1,5-diol and 1,4-hexadiene-1,6-diol; two hydroxyl groups such as cresol and naphthalenediol And aromatic hydrocarbons.

A C2-C20 (preferably 2-10, more preferably 4-6) hydrocarbon having two hydroxyl groups and at least one ether bond has at least one ether bond in the hydrocarbon chain ( Preferably it is 1-5, more preferably 1-3, but it may be a saturated hydrocarbon or an unsaturated hydrocarbon. Further, it may be a linear or branched chain or may be cyclic. The cyclic hydrocarbon includes aromatic hydrocarbons (however, in the case of aromatic hydrocarbons, the number of carbon atoms is 6 to 20). Specific examples of the C2-C20 hydrocarbon having two hydroxyl groups and at least one ether bond include diethylene glycol and triethylene glycol.

A C2-C20 (preferably 2-10, more preferably 4-6) hydrocarbon having 2 hydroxyl groups and 1-3 carboxyl groups has 1 to 3 carboxyl groups (preferably, 1), it may be a saturated hydrocarbon or an unsaturated hydrocarbon. Further, it may be a linear or branched chain or may be cyclic (however, in the case of a cyclic hydrocarbon, it is a hydrocarbon having 3 to 20 carbon atoms). The cyclic hydrocarbon includes aromatic hydrocarbons (however, in the case of aromatic hydrocarbons, the number of carbon atoms is 6 to 20). Here, the location where the hydrocarbon has a carboxyl group is not particularly limited, and any location of the hydrocarbon such as a terminal (end of the hydrocarbon chain), a side chain (chain branched from the hydrocarbon chain) or the like may be used. Absent.

Specific examples of the C2-C20 hydrocarbon having 2 hydroxyl groups and 1 to 3 carboxyl groups include dimethylolbutyric acid and dimethylolpropionic acid.

The polymer hydrocarbon having two hydroxyl groups is a hydrocarbon polymer compound, which may be a saturated hydrocarbon or an unsaturated hydrocarbon. Further, it may be a linear or branched chain, or may contain a cyclic structure.

As the molecular weight of the high molecular hydrocarbon, the weight average molecular weight is preferably 200 to 10,000 from the viewpoint of the reaction efficiency between the dicarboxylic anhydride moiety of the grafted diene polymer and the hydroxyl group. More preferably, it is 500-2,000.
In addition, the weight average molecular weight of a high molecular weight hydrocarbon can be measured by standard polystyrene conversion based on the measured value by a gel permeation chromatography (GPC).

Specific examples of the polymer hydrocarbon include polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polycaprolactone diol, and the following formula (1):

(Wherein, k, l, m, and n represent the number of repeating units), and the like.

Among them, as the diol compound, ethylene glycol, butanediol, hexanediol, decanediol, diethylene glycol, triethylene glycol, propylene glycol, in particular, from the viewpoint that flexibility, fluidity, and resilience are remarkably improved. More preferably, it is at least one selected from the group consisting of dimethylolbutyric acid, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, polybutadiene diol, and polycaprolactone diol, ethylene glycol, 1,4-butanediol, dimethylol butyric acid More preferably, it is at least one selected from the group consisting of dimethylolpropionic acid, and triethylene glycol, 1,4-butanediol, dimethylolbutyrate And particularly preferably at least one selected from the group consisting of dimethylolpropionic acid.

The polymer in the golf ball resin composition 4 is prepared by reacting the grafted diene polymer and the diol compound using a known method, and the carboxyl group and (anhydrous) dicarboxyl group in the obtained reaction product are contained in the polymer. Obtained by summing. Here, when the reaction product has no (anhydrous) dicarboxyl group, the “carboxyl group and (anhydrous) dicarboxyl group in the obtained reaction product” are “the obtained reaction product. In the polymer in the golf ball resin composition 4, the notation does not mean that the reaction product always has a carboxyl group and an (anhydrous) dicarboxyl group. Absent.

For example, by dissolving the diene polymer in an organic solvent, adding a predetermined amount of (anhydrous) dicarboxylic acid such as (anhydrous) maleic acid, and heating and reacting in the presence of an organic peroxide or a polymerization inhibitor. Grafted diene polymers having (anhydrous) dicarboxyl groups are obtained. Next, a reaction product having a carboxyl group and a (anhydrous) dicarboxyl group is obtained by adding the diol compound thereto and causing a reaction by heating. In addition, although the reaction conditions of the heat reaction of the grafted diene polymer and the diol compound can be appropriately set, for example, the reaction can be performed by kneading both at 110 to 160 ° C. for 1 to 8 hours. Then, the said polymer can be adjusted by neutralizing the carboxyl group and (anhydrous) dicarboxyl group in the obtained reaction product using an inorganic metal compound. The neutralization of the carboxyl group and the (anhydrous) dicarboxyl group can be carried out by melting the reaction product, adding a predetermined amount of an inorganic metal compound to the melt, and kneading. In addition, as an inorganic metal compound, the thing similar to the above can be used conveniently, for example.
Thus, the carboxyl group and (anhydrous) dicarboxyl group in the reaction product of the grafted diene polymer and the diol compound are selected from the group consisting of Na ⁺ , Mg ²⁺ , Ca ²⁺ , and Zn ^2+. It is also one of the preferred embodiments of the present invention to be neutralized by at least one metal ion.

The content of the (anhydrous) dicarboxylic acid in 100% by mass of the grafted diene polymer is preferably 2% by mass or more, and more preferably 4% by mass or more. The content is preferably 30% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. By adjusting within the above range, good resilience can be obtained.

In the grafted diene polymer, the content ratio of the diene polymer and the (anhydrous) dicarboxylic acid (diene polymer / (anhydrous) dicarboxylic acid (mass ratio)) is 1/0 from the viewpoint of the effect of the present invention. 0.041 to 1 / 0.176 is preferable, and 1 / 0.041 to 1 / 0.111 is more preferable.

In the synthesis of the polymer, the charging ratio of the grafted diene polymer to the diol compound is 0.20 to diol compound relative to the (anhydrous) dicarboxyl group in the grafted diene polymer. It is preferably 0.70 molar equivalent, more preferably 0.25 to 0.60 molar equivalent, and still more preferably 0.40 to 0.55 molar equivalent.

The content of carboxyl group and (anhydrous) dicarboxyl group in the reaction product obtained by reacting the grafted diene polymer with the diol compound is preferably 4 to 50% by mass. More preferably, it is 4-20 mass%, More preferably, it is 4-10 mass%.
The content of the carboxyl group and (anhydrous) dicarboxyl group can be calculated as follows.
Carboxyl group content (mass%) = (2 × ([(anhydrous) dicarboxyl group (mole) in grafted diene polymer]-[diol compound (mole)]) + ([diol compound (mole)] × [Number of carboxyl groups of diol compound molecule))) × 6,005 / [weight of reaction product (g)]
* 1 The content (mass%) of (anhydrous) dicarboxyl group is calculated based on 2 carboxyl groups.
* 2 Carboxyl group is regarded as the same molecular weight as acetic acid (CH ₃ COOH), and the content (mass%) is calculated.

The neutralization degree of the carboxyl group and (anhydrous) dicarboxyl group in the polymer is preferably 20% or more, more preferably 50% or more, and still more preferably 80% or more. Moreover, 300% or less is preferable, 200% or less is more preferable, and 100% or less is still more preferable. By adjusting within the above range, good resilience can be obtained.
In addition, the neutralization degree of a carboxyl group and (anhydrous) dicarboxyl group is a neutralized carboxyl group and (anhydrous) dicarboxyl group with respect to the total number of moles of the carboxyl group, (anhydrous) dicarboxyl group contained in the polymer. The number of moles.

The degree of neutralization is calculated from the amount of raw material charged. For example, the polymer is melted in tetrahydrofuran when heated and titrated with a prescribed concentration of potassium hydroxide in a heated state. The number of moles of neutralized carboxyl group ([COOH]) and non-neutralized (anhydrous) dicarboxyl group ([COOCO] or [(COOH) ₂ ]) and neutralized carboxyl group ([COOM]) calculated by metal analysis And the number of moles of the neutralized (anhydrous) dicarboxyl group ([(COOM) ₂ ]) can be calculated by the following formula.
Degree of neutralization (mol%) = ([COOM] + [(COOM) ₂ ]) / ([COOH] + [COOCO] + [(COOH) ₂ ] + [COOM] + [(COOM) ₂ ]) × 100
The metal analysis can be performed by the same method as described above, for example.

[Second Golf Ball Resin Composition]
The resin composition for golf balls of the second aspect of the present invention comprises (A) a diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more, and (B) Binary Copolymer of Olefin and C3-C8 α, β-Unsaturated Carboxylic Acid (b-1), Binary Copolymer of Olefin and C3-C8 α, β-Unsaturated Carboxylic Acid Neutralized product of polymer metal ion (b-2), terpolymer of olefin, α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and α, β-unsaturated carboxylic acid ester (b- 3) and a metal ion neutralized product (b-4) of a terpolymer of an olefin, an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α, β-unsaturated carboxylic acid ester. And at least one selected from the group consisting of:

As the resin component, the (B) component is further grafted with (anhydrous) dicarboxylic acid, and the diene polymer having a 1,4-cis structure content of 41% by mass or more, for example, a predetermined 1,4-cis It is possible to obtain good flexibility, fluidity and resilience by blending a diene polymer grafted (added) with (anhydrous) dicarboxylic acid at an arbitrary position of a polymer such as polybutadiene having a structural amount. it can.

The diene polymer having (A) component (anhydrous) dicarboxylic acid grafted (added) and having a 1,4-cis structure content of 41% by mass or more is obtained from the first golf ball resin composition 3. Since it is the same as that of a diene polymer, the detailed description is abbreviate | omitted.

In 100% by mass of the component (A), the content of the (A) (anhydrous) dicarboxylic acid is preferably 1% by mass or more, and more preferably 13% by mass or more. The content is preferably 45% by mass or less, and more preferably 41% by mass or less. The content is particularly preferably 3% by mass. By adjusting within the above range, good resilience can be obtained.

The amount of the component (A) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the component (B). Moreover, 70 mass parts or less are preferable. By adjusting within the above range, good resilience can be obtained.

The component (B) is not particularly limited, and a conventionally known component can be used as long as it contains at least one of (b-1) to (b-4). Especially, it is preferable to contain (b-2) or (b-4).

(B) As an olefin of a component, a C2-C8 olefin is preferable. Olefin is an aliphatic unsaturated hydrocarbon having one double bond in the molecule. Examples of the olefin having 2 to 8 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene and the like. Of these, ethylene and propylene are preferable, and ethylene is more preferable. Olefin can be used alone or in combination of two or more.

(B) Component C3-C8 α, β-unsaturated carboxylic acid includes acrylic acid, methacrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid (trans-2-butenoic acid), isocrotonic acid (Cis-2-butenoic acid), sorbic acid, citraconic acid, mesaconic acid and the like. Of these, acrylic acid, methacrylic acid, and (anhydrous) maleic acid are preferable from the viewpoints of flexibility, fluidity, and resilience.

(B) Component α, β-unsaturated carboxylic acid ester includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid (trans-2-butenoic acid), isocrotonic acid (cis-2-butenoic acid) Methyl, ethyl, propyl, n-butyl, isobutyl ester, etc., such as sorbic acid, citraconic acid, and mesaconic acid. Of these, acrylic acid esters and methacrylic acid esters are preferable from the viewpoints of flexibility, fluidity, and resilience.

In 100% by mass of the component (B), the content of the olefin is preferably 30% by mass or more, more preferably 47% by mass or more, and further preferably 55% by mass or more. The content is preferably 96% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. By adjusting within the above range, good resilience can be obtained.

In 100% by mass of the component (B), the content of the α, β-unsaturated carboxylic acid is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more. The content is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. By adjusting within the above range, good resilience can be obtained.

In 100% by mass of the component (B), the content of the α, β-unsaturated carboxylic acid ester is preferably 0% by mass or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more. The content is preferably 40% by mass or less, more preferably 32% by mass or less, and still more preferably 20% by mass or less. By adjusting within the above range, good resilience can be obtained.

In (b-2) and (b-4), the carboxyl group in the copolymer is neutralized with an inorganic metal compound. In this case, the resin composition preferably contains at least one metal ion selected from the group consisting of Na ⁺ , Mg ²⁺ , Ca ²⁺ , and Zn ²⁺ as the component (C).

The neutralization degree of the carboxyl group of the component (B) is preferably 50% or more, and more preferably 80% or more. Moreover, 500% or less is preferable, 300% or less is more preferable, and 150% or less is still more preferable. By adjusting within the above range, good resilience can be obtained.

The product (mass% ·%) of the content of the α, β-unsaturated carboxylic acid in 100% by mass of the component (B) and the neutralization degree of the carboxyl group is preferably 750 to 5500, 1000 to 3000 is more preferable, and 1200 to 2000 is still more preferable. The effect of this invention can fully be exhibited as it exists in the said range.

Each polymer of the component (B) can be synthesized by a known method, and commercially available products can also be used.

The resin composition for golf balls of the second aspect of the present invention can be obtained, for example, by adding a predetermined amount of the component (A) to the component (B) and kneading.

(Other)
The resin composition for a golf ball of the present invention further includes a pigment component such as a white pigment (for example, titanium oxide), a blue pigment, a weight adjuster, a dispersant, an anti-aging agent, an ultraviolet absorber, a light stabilizer, and a fluorescent material. Further, a fluorescent brightening agent or the like may be contained within a range that does not impair the performance of the golf ball. Moreover, the resin composition for golf balls of the present invention may use a fatty acid and / or a metal salt thereof in combination as long as the effects of the present invention are not impaired.

Content of the said white pigment (for example, titanium oxide) becomes like this. Preferably it is 0.5 mass part or more with respect to 100 mass parts of resin components, More preferably, it is 1 mass part or more. The content is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. By setting it as 0.5 mass part or more, concealment property can be provided to the obtained golf ball constituent member. On the other hand, if it exceeds 10 parts by mass, the durability of the resulting golf ball may be reduced.

The resin composition for golf balls of the present invention can be obtained, for example, by dry blending the above components. Further, the dry blended mixture may be extruded to be pelletized. For dry blending, for example, it is preferable to use a mixer capable of blending pellet-shaped raw materials, and more preferably a tumbler type mixer. For the extrusion, a known extruder such as a single screw extruder, a twin screw extruder, or a twin screw single screw extruder can be used.

In the golf ball resin composition of the present invention, the spin-lattice relaxation time (T1) of ¹³ C nuclei observed by a solid high-resolution carbon nuclear magnetic resonance method (NMR method) is preferably 15 seconds or less, and 12 seconds or less. Is more preferable, 10 seconds or less is still more preferable, and 8 seconds or less is still more preferable.

In addition, the golf ball resin composition of the present invention is stored when measured in a tensile mode using a dynamic viscoelastic device under conditions of an excitation frequency of 10 Hz, a temperature of 12 ° C., and a measurement strain of 0.05%. It is preferable that the elastic modulus E ′ (Pa) and the loss elastic modulus E ″ (Pa) satisfy the following formula.
By satisfying the following formula, the resin composition for a golf ball has high resilience while maintaining softness at a high level. In the following formula, log is a common logarithm.
log (E ′ / E ″ ² ) ≧ −6.55

It is considered that the resilience increases as the storage elastic modulus E ′ (Pa) increases and the loss elastic modulus E ″ (Pa) decreases. Also, as the storage elastic modulus E ′ (Pa) increases, the hardness also increases. In the above equation, the numerator is the first power of the storage elastic modulus E ′, whereas the denominator is the second power of the loss elastic modulus E ″. Rather than increasing the thickness, reducing the loss elastic modulus E ″ means that the effect of improving the resilience is greater. In other words, to increase the resilience without hardening the material, E ″ is decreased and the deformation is reduced. It is thought that it is necessary to reduce the energy loss at the time, but in the present invention, as the molecular mobility is increased as described above, it is possible to smoothly deform with respect to the stress. Will improve It is.

The log (E ′ / E ″ ² ) is preferably −6.23 or more, more preferably −6.02 or more, and further preferably −5.89 or more. Also, the log (E ′ / E ″ ² ). Although the upper limit of is not specifically limited, -5.24 or less is preferable and -5.40 or less is more preferable. This is because when the log (E ′ / E ″ ² ) becomes −5.25, the coefficient of restitution approaches the maximum value of 1. As measurement conditions for dynamic viscoelasticity, excitation frequency: 10 Hz, temperature: 12 The measurement condition of ° C. is adopted based on the following reason: The contact time between the golf ball and the collision rod (metal cylinder) in the measurement of the coefficient of restitution at 40 m / s is 500 μsec. Is a deformation of a frequency of several thousand Hz, and based on the frequency / temperature conversion rule of general ionomer resin, the dynamic measurement is performed under the measurement conditions of temperature: room temperature and excitation frequency: several thousand Hz. Viscoelasticity corresponds to dynamic viscoelasticity measured under measurement conditions of temperature: 12 ° C. and excitation frequency: 10 Hz.

The melt flow rate (190 ° C. × 2.16 kg) of the golf ball resin composition of the present invention is preferably 1.0 g / 10 min or more, more preferably 1.5 g / 10 min or more, and further preferably 2.0 g / 10 min. That's it. The melt flow rate is preferably 100 g / 10 min or less, more preferably 80 g / 10 min or less, still more preferably 50 g / 10 min or less. If it is in the said range, the moldability to a golf ball structural member will be favorable.

The rebound resilience of the golf ball resin composition is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, and particularly preferably 75% or more. By using 60% or more of the golf ball resin composition, a golf ball having excellent resilience (flying distance) can be obtained. The rebound resilience is a rebound resilience measured by molding a golf ball resin composition into a sheet shape, and is measured by a measurement method described later.

The slab hardness of the golf ball resin composition is preferably 5 or more in Shore D hardness, more preferably 10 or more, and still more preferably 20 or more. The slab hardness (Shore D hardness) is preferably 50 or less, more preferably 30 or less, and even more preferably 25 or less. By using five or more golf ball resin compositions, a golf ball having excellent resilience (flying distance) can be obtained. On the other hand, a golf ball having excellent durability can be obtained by using a resin composition for golf balls of 50 or less. Here, the slab hardness of the golf ball resin composition is a hardness measured by molding the golf ball resin composition into a sheet shape, and is measured by a measurement method described later.

In addition, in the above, when it is simply described as “the golf ball resin composition of the present invention”, it means that it is an explanation for the entire first and second golf ball resin compositions of the present invention. Yes.

〔Golf ball〕
The golf ball of the present invention is not particularly limited as long as it has a constituent member formed from the golf ball resin composition. For example, a one-piece golf ball; a two-piece golf ball having a single-layer core and a cover disposed so as to cover the single-layer core; a center and a single-layer intermediate layer disposed so as to cover the center A three-piece golf ball having a core formed of: and a cover disposed so as to cover the core; or a core formed of a center and one or more intermediate layers disposed so as to cover the center. Any of the constituent members constituting a multi-piece golf ball (including the three-piece golf ball) having a cover disposed to cover the core is formed from the golf ball resin composition of the present invention. A golf ball can be mentioned. Among these, a golf ball having at least one core and a cover covering the core, wherein at least one layer of the core is formed from the resin composition for golf balls, or one-piece golf An embodiment in which the golf ball body of the ball is formed from the golf ball resin composition is preferable. In particular, a two-piece golf ball having a single layer core and a cover disposed so as to cover the single layer core, wherein the single layer core is formed from the golf ball resin composition, Or a multi-piece golf ball having a core comprising a center and one or more intermediate layers disposed so as to cover the center, and a cover disposed so as to cover the core; However, the aspect currently formed from the said resin composition for golf balls is preferable.

Hereinafter, an example of the golf ball of the present invention is a two-piece golf ball having a core and a cover disposed so as to cover the core, and the core is formed from the above-described resin composition for golf balls. However, the present invention is not limited to such an embodiment.

The core is molded, for example, by injection molding the above-described golf ball resin composition. Specifically, a golf ball resin composition heated and melted at 160 to 260 ° C. is poured into a mold clamped at a pressure of 1 to 100 MPa in 1 to 100 seconds, and cooled down for 30 to 300 seconds. It is preferable to perform by opening.

The core is preferably spherical. When the shape of the core is not spherical, the thickness of the cover becomes non-uniform, and as a result, there may be a portion where the cover performance is partially reduced.

The core has a diameter of preferably 39.00 mm or more, more preferably 39.25 mm or more, and still more preferably 39.50 mm or more. The diameter is preferably 42.37 mm or less, more preferably 42.22 mm or less, and still more preferably 42.07 mm or less. If it is 39.00 mm or more, the thickness of the cover layer will not be too thick, and as a result, the resilience will be good. On the other hand, if it is 42.37 mm or less, the cover layer does not become too thin, and the protective function of the cover is sufficiently exhibited.

When the core has a diameter of 39.00 to 42.37 mm, the amount of compressive deformation (the amount by which the core contracts in the compression direction) from when the initial load 98N is applied to when the final load 1275N is applied is preferably 1. It is 00 mm or more, more preferably 1.10 mm or more. The amount of compressive deformation is preferably 5.00 mm or less, more preferably 4.90 mm or less, and still more preferably 4.80 mm or less. If it is 1.00 mm or more, the feel at impact is good, and if it is 5.00 mm or less, the resilience is good.

The surface hardness of the core is preferably 20 or more in Shore D hardness, more preferably 25 or more, and still more preferably 30 or more. The surface hardness (Shore D hardness) is preferably 70 or less, and more preferably 69 or less. By setting it to 20 or more, the core does not become too soft and good resilience can be obtained. Moreover, by setting it as 70 or less, a core does not become hard too much and a favorable shot feeling is obtained.

The core has a center hardness of preferably 5 or more in Shore D hardness, more preferably 7 or more, and still more preferably 10 or more. If it is less than 5, it may become too soft and the resilience may decrease. Further, the center hardness of the core is preferably 50 or less in Shore D hardness, more preferably 48 or less, and still more preferably 46 or less. If it exceeds 50, it becomes too hard and the feel at impact tends to be lowered. In the present invention, the center hardness of the core means a hardness measured by a spring type hardness tester Shore D type at a center point of the cut surface by cutting the core into two equal parts.

It is also preferable that the core contains a filler. The filler is mainly blended as a weight regulator for adjusting the density of the golf ball obtained as a final product to a range of 1.0 to 1.5, and may be blended as necessary. Examples of the filler include inorganic fillers such as zinc oxide, barium sulfate, calcium carbonate, magnesium oxide, tungsten powder, and molybdenum powder. The blending amount of the filler is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more with respect to 100 parts by mass of the resin component. The amount is preferably 30 parts by mass or less, more preferably 20 parts by mass or less. If the amount is less than 0.5 parts by mass, it is difficult to adjust the weight. If the amount exceeds 30 parts by mass, the weight fraction of the resin component tends to be small, and the resilience tends to decrease.

The golf ball cover of the present invention is preferably formed from a cover composition containing a resin component. Examples of the resin component include various resins such as urethane resins such as ionomer resins, polyester resins, thermoplastic urethane resins or two-component curable urethane resins, and polyamide resins.

Examples of ionomer resins that can be used for golf ball covers include “Himilan (registered trademark)” (for example, Himilan 1555 (Na), Himilan 1557 (Zn), and Himilan, available from Mitsui DuPont Polychemical Co., Ltd.). 1605 (Na), High Milan 1706 (Zn), High Milan 1707 (Na), High Milan AM 7311 (Mg), High Milan AM 7329 (Zn), High Milan AM 7327 (Zn), High Milan 1855 (Zn), High Milan 1856 (Na), High Milan AM 7331 ( Na), etc. ", commercially available from DuPont, such as Surlyn (registered trademark) (for example, Surlyn 8945 (Na), Surlyn 9945 (Zn), Surlyn 8140 (Na), Surlyn 8150 (N ), Surlyn 9120 (Zn), Surlyn 9150 (Zn), Surlyn 6910 (Mg), Surlyn 6120 (Mg), Surlyn 7930 (Li), Surlyn 7940 (Li), Surlyn AD8546 (Li), Surlyn 6320 (Mg), Surlyn 8120 (Na), Surlyn 8320 (Na), Surlyn 9320 (Zn), Surlyn 9320W (Zn), etc.) "," Iotek (registered trademark) "(for example, commercially available from ExxonMobil Chemical Co., Ltd.) It is preferable to use “Iotech 8000 (Na), Iotech 8030 (Na), Iotech 7010 (Zn), Iotech 7030 (Zn), Iotech 7510 (Zn), Iotech 7520 (Zn), etc.)”. In addition, Na, Zn, Mg, etc. described in parentheses after the trade name indicate the type of neutralized metal ion. These ionomer resins may be used alone or in combination of two or more.
In addition, a thermoplastic polyamide elastomer marketed by Arkema Co., Ltd. under the trade name “Pebax (registered trademark)” (for example, “Pebax 2533”), and from Toray DuPont, trade name “Hytrel” (registered trademark) ( For example, a thermoplastic polyester elastomer commercially available under the name “Hytrel 3548”, “Hytrel 4047”), commercially available under the trade name “Elastollan (registered trademark)” (for example, “Elastollan XNY97A”) from BASF Japan Ltd. And the thermoplastic polyurethane elastomer, and the thermoplastic styrene elastomer marketed by Mitsubishi Chemical Corporation under the trade name “Lavalon (registered trademark)”. You may use the said resin component individually or in mixture of 2 or more types.

More preferably, the cover composition constituting the cover of the golf ball contains a polyurethane resin (including a polyurethane elastomer) or an ionomer resin as a resin component. The content of the polyurethane resin or ionomer resin in the resin component of the cover composition is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more.

In addition to the resin component described above, the cover composition includes pigment components such as white pigments (eg, titanium oxide), blue pigments, and red pigments, weight adjusters such as zinc oxide, calcium carbonate, and barium sulfate, dispersants, and aging. An inhibitor, an ultraviolet absorber, a light stabilizer, a fluorescent material, a fluorescent whitening agent, or the like may be contained within a range that does not impair the performance of the cover.

The content of the white pigment (for example, titanium oxide) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the resin component constituting the cover. The content is preferably 10 parts by mass or less, more preferably 8 parts by mass or less. By setting it as 0.5 mass part or more, concealment property can be provided to a cover. Moreover, when it exceeds 10 mass parts, durability of the cover obtained may fall.

The golf ball cover of the present invention may be molded by, for example, a compression molding method (preferably, a cover), in which a hollow shell-shaped shell is molded from a cover composition, and the core is covered with a plurality of shells. A method in which a hollow shell-shaped half shell is molded from the composition for coating and the core is covered with two half shells and compression molded), or an injection molding method in which the cover composition is directly injection molded onto the core. be able to.

When a cover composition is injection molded to form a cover, it may be injection molded using a pellet-shaped cover composition obtained by extrusion in advance, or a cover of a base resin component, pigment, etc. The materials may be dry blended and directly injection molded. As the upper and lower molds for forming the cover, it is preferable to use a cover mold having a hemispherical cavity and having a pimple and also serving as a hold pin in which a part of the pimple can advance and retreat. The cover can be formed by injection molding by projecting the hold pin, inserting the core, holding the cover, injecting the cover composition, and cooling. Specifically, a cover composition heated to 200 to 250 ° C. is injected in a mold clamped at a pressure of 9 to 15 MPa in 0.5 to 5 seconds, cooled for 10 to 60 seconds, and opened. It is preferable to carry out by doing.

When molding a cover, a depression called a dimple is usually formed on the surface. The total number of dimples formed on the cover is preferably 200 to 500. If it is less than 200, the dimple effect is difficult to obtain. On the other hand, if the number exceeds 500, the size of each dimple becomes small, and it is difficult to obtain the dimple effect. The shape (plan view shape) of the dimple formed is not particularly limited, and a circular shape; a polygon such as a substantially triangular shape, a substantially square shape, a substantially pentagonal shape, or a substantially hexagonal shape; Alternatively, two or more kinds may be used in combination.

The cover has a thickness of preferably 2.0 mm or less, more preferably 1.6 mm or less, still more preferably 1.2 mm or less, and particularly preferably 1.0 mm or less. If it is 2.0 mm or less, the resilience and feel at impact of the resulting golf ball will be better. The thickness of the cover is preferably 0.1 mm or more, more preferably 0.2 mm or more, and further preferably 0.3 mm or more. If it is less than 0.1 mm, molding of the cover may be difficult, and the durability and wear resistance of the cover may be reduced.

The golf ball body in which the cover is molded is preferably taken out from the mold and subjected to surface treatment such as deburring, washing, and sandblasting as necessary. Moreover, a coating film and a mark can also be formed if desired. Although the film thickness of a coating film is not specifically limited, 5 micrometers or more are preferable and 7 micrometers or more are more preferable. The film thickness is preferably 25 μm or less, and more preferably 18 μm or less. When the thickness is less than 5 μm, the coating tends to be worn away by continuous use, and when it exceeds 25 μm, the dimple effect is reduced and the flight performance of the golf ball tends to be reduced.

In the golf ball of the present invention, the amount of compressive deformation (the amount of contraction in the compression direction) when a final load of 1275N is applied from a state where an initial load of 98N is applied is preferably 2.0 mm or more, and 2.2 mm or more. More preferred. The amount of compressive deformation is preferably 4.0 mm or less, and more preferably 3.5 mm or less. A golf ball of 2.0 mm or more does not become too hard and has a good shot feeling. On the other hand, when the thickness is 4.0 mm or less, the resilience increases.

While the embodiment in which the golf ball resin composition of the present invention is used for the core has been described above, the golf ball resin composition of the present invention can also be used for the center, the intermediate layer, or the cover. When the center is formed from the golf ball resin composition of the present invention, as the material for forming the intermediate layer, for example, the resin component exemplified as the cover material can be used.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

[Evaluation method]
(1) Slab hardness (Shore D hardness)
Using the golf ball resin composition, a sheet having a thickness of about 2 mm was produced by hot press molding and stored at 23 ° C. for 2 weeks. An automatic rubber hardness tester P1 type manufactured by Kobunshi Keiki Co., Ltd. equipped with a spring type hardness tester Shore D type as defined in ASTM-D2240 in a state where three or more sheets are stacked so as not to affect the measurement substrate. It measured using.

(2) Melt flow rate (MFR) (g / 10 min)
MFR was measured according to JIS K7210 using a flow tester (manufactured by Shimadzu Corporation, Shimadzu flow tester CFT-100C). The measurement was performed under the conditions of a measurement temperature of 190 ° C. and a load of 2.16 kg.

(3) Rebound resilience (%)
A golf ball resin composition is used to produce a sheet having a thickness of about 2 mm by hot press molding, and by stacking six sheets punched into a circular shape having a diameter of 28 mm from the sheet, the thickness is about 12 mm and the diameter A 28 mm cylindrical test piece was prepared. A Rüpke-type rebound resilience test (test temperature and humidity 23 ° C., 50 RH%) was performed on this test piece. The test piece was prepared and tested in accordance with JIS K6255.

(4) Amount of compressive deformation The amount of deformation in the compression direction (the amount by which the spherical body contracts in the compression direction) from when the initial load 98N is applied to the spherical body to when the final load 1275N is applied was measured.

(5) Coefficient of restitution 198.4 g of a metal cylinder collides with each spherical body at a speed of 40 m / sec., And measures the speed of the cylinder and the golf ball before and after the collision. The coefficient of restitution was calculated. The measurement was performed on 12 pieces for each spherical body, and the average value was used as the restitution coefficient of each spherical body.

(6) Feeling of hitting ball 10 amateur golfers (advanced players) performed an actual hitting test using a driver, and evaluated the feeling of each hitting ball according to the following criteria. Of the 10 evaluations, the highest evaluation was the shot feel of the golf ball.
Excellent evaluation criteria: Feeling is good with little impact.
Good: Normal.
Inferior: The impact is great and the feeling is bad.

(7) Apparatus for measuring spin-lattice relaxation time (T ₁ ) of ¹³ C nuclei observed by solid high-resolution carbon nuclear magnetic resonance (NMR) method: Bruker Avance 400
Measurement method: Torchia method by _{T 1} relaxation time measurement measurement frequency: 100.6256207MHz
Measurement temperature: room temperature Reference material: adamantane magic angle rotation speed: 5000 Hz
Pulse width: 4.80 μsec
Contact time: 2000 μsec
Pulse interval: 1 μsec, 100 msec, 500 msec, 1 sec, 2 sec, 3 sec, 4 sec, 6 sec, 8 sec, 10 sec, 12 sec, 15 sec, 20 sec, 40 sec, 80 sec, 120 sec
Magnetic field strength: 9.4T

(8) Measurement of storage elastic modulus E ′ (Pa) and loss elastic modulus E ″ (Pa) The storage elastic modulus E ′ (Pa) and loss elastic modulus E ″ (Pa) of the golf ball resin composition are as follows. Measured with
Apparatus: Dynamic viscoelasticity measuring apparatus Rheogel-E4000 manufactured by UBM Co., Ltd.
Measurement sample: A sheet having a thickness of 2 mm was produced from the resin composition for golf balls by press molding, and a sample piece was cut out from the sheet so as to have a width of 4 mm and a distance between clamps of 20 mm.
Measurement mode: Tensile measurement temperature: 12 ° C
Excitation frequency: 10 Hz
Measurement strain: 0.05%

(Preparation of BD / AA copolymer (1-1)) cis content 20%, acid content 15%
85 parts by mass of polybutadiene having an acrylate group added thereto by a known method to polybutadiene having OH groups at both ends (cis content: 20% by mass, R-45HT manufactured by Idemitsu Kosan Co., Ltd.), and 27 parts by mass of t-butyl acrylate And 0.005 part by mass of ethyl α-bromobutyrate, copper (II) chloride / tris [2- (dimethylamino) ethyl] amine / 2-ethylhexanoate / anisole = 1/5 / 0.01 mass part of 10/500 mixed solution was added, and it heated at 70 degreeC for 8 hours. Thereafter, 108 parts by mass of trifluoroacetic acid was added and stirred at room temperature for 12 hours. The obtained product was washed with 10 times the amount of ethanol and dried at 100 ° C. for 16 hours or more to obtain a BD / AA copolymer (1 -1) was produced.

(Preparation of BD / AA copolymer (1-2)) cis content 20%, acid content 8%
The BD / AA copolymer was prepared in the same manner as in the preparation of the copolymer (1-1) except that the blending amount of the polybutadiene provided with the acrylate group was changed to 92 parts by mass and the blending amount of t-butyl acrylate was changed to 14.2 parts by mass. (1-2) was produced.

(Preparation of BD / AA copolymer (1-3)) cis content 20%, acid content 50%
The BD / AA copolymer (1) was prepared in the same manner as in the preparation of the copolymer (1-1) except that the blending amount of the polybutadiene having the acrylate group was changed to 50 parts by mass and the blending amount of t-butyl acrylate was changed to 89 parts by mass. -3) was produced.

(Preparation of BD / AA copolymer (1-4)) cis content 10%, acid content 15%
Except for changing polybutadiene having OH groups at both ends (cis content: 20% by mass) to polybutadiene having OH groups at both ends (cis content: 10% by mass, G-3000 manufactured by Nippon Soda Co., Ltd.) A BD / AA copolymer (1-4) was produced in the same manner as in the production of the copolymer (1-1).

[Preparation of spherical body (core) (other than Table 1 Comparative Example 1-2)]
As shown in Tables 1 to 6, the blended materials were dry blended, mixed by a twin-screw kneading extruder, and extruded into cold water in a strand shape. The extruded strand was cut with a pelletizer to prepare a pelletized golf ball resin composition. The extrusion conditions were a screw diameter of 45 mm, a screw rotation speed of 200 rpm, and a screw L / D = 35, and the blend was heated to 160-230 ° C. at the die position of the extruder. The obtained pellet-shaped golf ball resin composition was injection molded at 220 ° C. to obtain a spherical body (core) having a diameter of 40 mm.

[Production of Sphere (Core) (Table 1 Comparative Example 1-2)]
The compounding material shown in Comparative Example 1-2 of Table 1 was kneaded with a kneading roll and heated and pressed at 170 ° C. for 20 minutes in an upper and lower mold having hemispherical cavities to obtain a spherical body (core) having a diameter of 40 mm.

In addition to the BD / AA copolymers (1-1) to (1-4), the raw materials used in Tables 1 to 6 are as follows.
Nukurel N1560: manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass)
Butadiene rubber: BR730 manufactured by JSR Corporation (cis content: 95% by mass)
Magnesium hydroxide: Sodium hydroxide manufactured by Wako Pure Chemical Industries, Ltd .: Zinc oxide manufactured by Wako Pure Chemical Industries, Ltd .: Calcium hydroxide manufactured by Sigma-Aldrich Co., Ltd .: Lithium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd .: Potassium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd .: Wako Pure Chemical Industries, Ltd. Copper hydroxide: Sigma Aldrich Co. Iron chloride (III): Sigma Aldrich Co. Zinc acrylate: Sigma Aldrich Co.

From the results of Tables 1 to 6, the carboxyl groups present in the reaction product of the diene polymer having α, β-unsaturated carbonyl groups at both ends and the unsaturated carboxylic acid compound having 2 to 18 carbon atoms are The resin compositions of the examples produced by adding together were improved in flexibility, fluidity, and resilience compared with the existing materials of the comparative examples. In addition, the performance could be adjusted by adjusting the amount of unsaturated carboxylic acid compound, cis content, inorganic metal compound type, degree of neutralization, and the like.

(Preparation of BD / AA copolymer (2-1)) cis content 20%, acid content 15%
85 parts by mass of polybutadiene obtained by reacting polybutadiene having OH groups at both ends (cis content: 20% by mass, R-45HT manufactured by Idemitsu Kosan Co., Ltd.) with bromoisobutyric acid bromide by a known method, and t-butyl acrylate 27 And 200 parts by mass of anisole, 2.3 parts by mass of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 2.3 parts by mass of copper (I) bromide, 0.2 parts by mass of copper (II) bromide was added and heated at 60 ° C. for 18 hours. After purifying the obtained polymer by reprecipitation, 200 parts by mass of tetrahydrofuran, 37 parts by mass of trimethylsilyl azide, 20 parts by mass of potassium fluoride, and 2 parts by mass of tetrafluoroammonium fluoride were added and stirred at room temperature for 24 hours. After the obtained polymer solution was concentrated through a silica gel short column, 400 parts by mass of tetrahydrofuran, 4 parts by mass of dipropargyl ether, 10 parts by mass of copper (I) bromide, N, N, N ′, N ″, N '' -Pentamethyldiethylenetriamine (5 parts by mass) was added, and the mixture was stirred at room temperature for 24 hours. The obtained polymer solution was concentrated through a silica gel short column, 400 parts by mass of methylene chloride and 50 parts by mass of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 12 hours. BD / AA copolymer (2-1) was prepared by washing at 100 ° C. and drying for 16 hours or more.

(Preparation of BD / AA copolymer (2-2)) cis content 20%, acid content 8%
The BD / BD was prepared in the same manner as in the preparation of the copolymer (2-1), except that the amount of polybutadiene reacted with the bromoisobutyric acid bromide was changed to 92 parts by mass and the amount of t-butyl acrylate was changed to 14.2 parts by mass. AA copolymer (2-2) was produced.

(Preparation of BD / AA copolymer (2-3)) cis content 20%, acid content 50%
The BD / AA copolymer was prepared in the same manner as in the preparation of the copolymer (2-1) except that the blending amount of polybutadiene reacted with the bromoisobutyric acid bromide was changed to 50 parts by mass and the blending amount of t-butyl acrylate was changed to 89 parts by mass. (2-3) was produced.

(Preparation of BD / AA copolymer (2-4)) cis content 10%, acid content 15%
Except for changing polybutadiene having OH groups at both ends (cis content: 20% by mass) to polybutadiene having OH groups at both ends (cis content: 10% by mass, G-3000 manufactured by Nippon Soda Co., Ltd.) A BD / AA copolymer (2-4) was produced in the same manner as in the production of the copolymer (2-1).

[Production of spherical body (core) (other than Table 7 Comparative Example 2-2)]
As shown in Tables 7 to 12, the blended materials were dry blended, mixed by a twin-screw kneading type extruder, and extruded into cold water in a strand shape. The extruded strand was cut with a pelletizer to prepare a pelletized golf ball resin composition. The extrusion conditions were a screw diameter of 45 mm, a screw rotation speed of 200 rpm, and a screw L / D = 35, and the blend was heated to 160-230 ° C. at the die position of the extruder. The obtained pellet-shaped golf ball resin composition was injection molded at 220 ° C. to obtain a spherical body (core) having a diameter of 40 mm.

[Production of Sphere (Core) (Table 7 Comparative Example 2-2)]
The compounding material shown in Comparative Example 2-2 in Table 7 was kneaded with a kneading roll and heated and pressed at 170 ° C. for 20 minutes in an upper and lower mold having hemispherical cavities to obtain a spherical body (core) having a diameter of 40 mm.

In addition to BD / AA copolymers (2-1) to (2-4), the raw materials used in Tables 7 to 12 are as follows.
Nukurel N1560: manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass)
Butadiene rubber: BR730 manufactured by JSR Corporation (cis content: 95% by mass)
Magnesium hydroxide: Sodium hydroxide manufactured by Wako Pure Chemical Industries, Ltd .: Zinc oxide manufactured by Wako Pure Chemical Industries, Ltd .: Calcium hydroxide manufactured by Sigma Aldrich Co., Ltd .: Potassium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd .: Zinc acrylate manufactured by Wako Pure Chemical Industries, Ltd. : Sigma-Aldrich

From the results of Tables 7 to 12, the carboxyl groups present in the reaction product of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms The resin composition of the example produced by neutralizing the resin had improved flexibility, fluidity, and resilience compared to the existing material of the comparative example. In addition, the performance could be adjusted by adjusting the amount of unsaturated carboxylic acid compound, cis content, inorganic metal compound type, degree of neutralization, and the like.

[Production of spherical body (core) (other than Table 13 Comparative Example 3-2)]
As shown in Tables 13 to 18, the blended materials were dry blended, mixed by a twin-screw kneading type extruder, and extruded into cold water in a strand shape. The extruded strand was cut with a pelletizer to prepare a pelletized golf ball resin composition. The extrusion conditions were a screw diameter of 45 mm, a screw rotation speed of 200 rpm, and a screw L / D = 35, and the blend was heated to 160-230 ° C. at the die position of the extruder. The obtained pellet-shaped golf ball resin composition was injection molded at 220 ° C. to obtain a spherical body (core) having a diameter of 40 mm.

[Production of Sphere (Core) (Table 13 Comparative Example 3-2)]
The compounding material shown in Comparative Example 3-2 in Table 13 was kneaded with a kneading roll and heated and pressed at 170 ° C. for 20 minutes in an upper and lower mold having hemispherical cavities to obtain a spherical body (core) having a diameter of 40 mm.

The raw materials used in Tables 13 to 18 are as follows.
POLYVEST EP MA120: manufactured by Evonik Japan Co., Ltd., maleic anhydride-modified polybutadiene (cis content: 75 mass%, dicarboxylic anhydride content: 2 to 30 mass%)
RICON131MA5: manufactured by Clay Valley, maleic anhydride-modified polybutadiene (cis content: 35% by mass)
RICON156MA17: manufactured by Clay Valley, maleic anhydride-modified polybutadiene (cis content: 15% by mass)
TP049 modified with maleic anhydride: TP049 (manufactured by Asahi Kasei Kogyo Co., Ltd., transpolybutadiene) grafted with maleic anhydride by a known method (JP 2001-72626, JP-B-6-4751, etc.) (cis content: 11 (Mass%, trans content: 87 mass%, dicarboxylic anhydride content: 4 mass%)
Nukurel N1560: manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass)
Butadiene rubber: BR730 manufactured by JSR Corporation (cis content: 95% by mass)
Magnesium hydroxide: Sodium hydroxide manufactured by Wako Pure Chemical Industries, Ltd .: Zinc oxide manufactured by Wako Pure Chemical Industries, Ltd .: Calcium hydroxide manufactured by Sigma Aldrich Co., Ltd .: Potassium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd .: Zinc acrylate manufactured by Wako Pure Chemical Industries, Ltd. : Distilled water manufactured by Sigma-Aldrich: Wako Pure Chemical Industries

From the results shown in Tables 13 to 18, it exists in a diene polymer having a 1,4-cis structure content of 41% by mass or more obtained by grafting (anhydrous) dicarboxylic acid to the terminal and / or side chain (anhydrous). The resin composition of the example produced by neutralizing the dicarboxyl group had improved flexibility, fluidity, and resilience compared with the existing material of the comparative example. In addition, the performance could be adjusted by adjusting the amount of (anhydrous) dicarboxylic acid, the cis content, the inorganic metal compound species, the degree of neutralization, and the like.

[Production of spherical body (core) (other than Table 19 Comparative Example 4-5)]
After blending the components (B) and (C) for 15 minutes at 200 ° C. with a twin-screw kneading extruder with the formulation shown in Tables 19 to 22, the component (A) was added and Kneaded for a minute. Then, it extruded into cold water in the form of a strand. The extruded strand was cut with a pelletizer to prepare a pelletized golf ball resin composition. The extrusion conditions were a screw diameter of 45 mm, a screw rotation speed of 200 rpm, and a screw L / D = 35, and the blend was heated to 160-230 ° C. at the die position of the extruder. The obtained pellet-shaped golf ball resin composition was injection molded at 220 ° C. to obtain a spherical body (core) having a diameter of 40 mm.

[Production of Sphere (Core) (Table 19 Comparative Example 4-5)]
The compounding materials shown in Comparative Example 4-5 in Table 19 were kneaded with a kneading roll, and heated and pressed in an upper and lower mold having hemispherical cavities at 170 ° C. for 20 minutes to obtain a spherical body (core) having a diameter of 40 mm.

The raw materials used in Tables 19 to 22 are as follows.
POLYVEST EP MA120: manufactured by Evonik Japan Co., Ltd., maleic anhydride-modified polybutadiene (cis content: 75 mass%, dicarboxylic anhydride content: 4 mass%)
TP049 modified with maleic anhydride: TP049 (manufactured by Asahi Kasei Kogyo Co., Ltd., transpolybutadiene) grafted with maleic anhydride by a known method (JP 2001-72626, JP-B-6-4751, etc.) (cis content: 11 (Mass%, trans content: 87 mass%, dicarboxylic anhydride content: 4 mass%)
Nukurel N1560: manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass)
Nucleel AN4319: Mitsui-DuPont Polychemical Co., Ltd., ethylene / methacrylic acid / acrylic acid ester copolymer (methacrylic acid content: 8% by mass)
Nukurel N2060: manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene / methacrylic acid copolymer (methacrylic acid content: 20% by mass)
Butadiene rubber: BR730 manufactured by JSR Corporation (cis content: 95% by mass)
Magnesium hydroxide: Sodium hydroxide manufactured by Wako Pure Chemical Industries, Ltd .: Zinc oxide manufactured by Wako Pure Chemical Industries, Ltd .: Calcium hydroxide manufactured by Sigma Aldrich Co., Ltd .: Potassium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd .: Zinc acrylate manufactured by Wako Pure Chemical Industries, Ltd. : Sigma-Aldrich

From the results of Tables 19 to 22, as the component (A), a diene polymer having a 1,4-cis structure content of 41% by mass or more obtained by grafting (anhydrous) dicarboxylic acid to the terminal and / or side chain is used. The resin composition of the added example was improved in flexibility, fluidity, and resilience compared to the resin composition of the comparative example in which the component (A) was not added. In addition, the performance could be adjusted by adjusting the blending amount of the component (A), the degree of neutralization of the component (B), the inorganic metal compound type, and the like.

[Production of spherical body (core) (other than Table 23 Comparative Example 5-2)]
As shown in Tables 23 to 27, the blended materials were dry blended (however, in Examples 5-1 to 5-16, before all the blended materials were dry blended, the components (A) and (B) were previously prepared. The mixture was kneaded at 135 ° C. for 4 hours and allowed to react.), Was mixed by a twin-screw kneading type extruder and extruded into cold water as a strand. The extruded strand was cut with a pelletizer to prepare a pelletized golf ball resin composition. The extrusion conditions were a screw diameter of 45 mm, a screw rotation speed of 200 rpm, and a screw L / D = 35, and the blend was heated to 160-230 ° C. at the die position of the extruder. The obtained pellet-shaped golf ball resin composition was injection molded at 220 ° C. to obtain a spherical body (core) having a diameter of 40 mm.

[Production of Sphere (Core) (Table 23 Comparative Example 5-2)]
The compounding material shown in Comparative Example 5-2 in Table 23 was kneaded with a kneading roll and heated and pressed at 170 ° C. for 20 minutes in an upper and lower mold having a hemispherical cavity to obtain a spherical body (core) having a diameter of 40 mm.

[Content of carboxyl group and anhydrous dicarboxyl group]
The content (mass%) of the carboxyl group and the anhydrous dicarboxyl group was calculated as follows.
Carboxyl group content (mass%) = (2 × ([anhydrous dicarboxyl group in grafted diene polymer (mol)] − [diol compound (mol)]) + ([diol compound (mol)] × [ Number of carboxyl groups in the diol compound molecule])) × 6,005 / [weight of reaction product (g)]
* 1 The content (mass%) of the anhydrous dicarboxyl group was calculated by considering it as 2 carboxyl groups.
* 2 The carboxyl group was regarded as having the same molecular weight as acetic acid (CH ₃ COOH), and the content (% by mass) was calculated.

The raw materials used in Tables 23 to 27 are as follows.
POLYVEST EP MA120: manufactured by Evonik Japan Co., Ltd., maleic anhydride-modified polybutadiene (cis content: 75 mass%, dicarboxylic anhydride content: 2 to 30 mass%)
Nukurel N1560: manufactured by Mitsui DuPont Polychemical Co., Ltd., ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass)
Butadiene rubber: BR730 manufactured by JSR Corporation (cis content: 95% by mass)
Dimethylolbutyric acid: Tokyo Kasei Co., Ltd. ethylene glycol: Tokyo Kasei Co., Ltd. 1,4-butanediol: Tokyo Kasei Co., Ltd. dimethylolpropionic acid: Tokyo Kasei Co., Ltd. triethylene glycol: Tokyo Kasei Co., Ltd. magnesium hydroxide: Wako Pure Chemical Industries Sodium hydroxide manufactured by: Wako Pure Chemical Industries, Ltd. Zinc oxide: Sigma Aldrich, calcium hydroxide: Tokyo Chemical Industry, zinc acrylate: Sigma Aldrich, distilled water: Wako Pure Chemical Industries, Ltd.

From the results of Tables 23 to 27, the carboxyl group and (anhydrous) dicarboxyl group present in the reaction product of the diene polymer and the diol compound obtained by grafting (anhydrous) dicarboxylic acid to the terminal and / or side chain are shown. The resin composition of the example produced by neutralization was improved in flexibility, fluidity, and resilience compared with the existing material of the comparative example. In addition, the performance could be adjusted by adjusting the diol compound species, the amount of diol compound charged, the degree of neutralization, the inorganic metal compound species, and the like.

According to the present invention, a golf ball resin composition excellent in resilience, flexibility, and fluidity can be obtained. By using the resin composition, golf excellent in resilience, feel at impact, and productivity. Can provide balls.

Claims (24)

A golf ball resin composition comprising a polymer having a diene polymer moiety and a carboxylic acid moiety, wherein the carboxyl group derived from the carboxylic acid moiety is neutralized. The polymer is derived from the unsaturated carboxylic acid compound in the reaction product of a diene polymer having α, β-unsaturated carbonyl groups at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. The golf ball resin composition according to claim 1, which is obtained by neutralizing a carboxyl group. The diene polymer is a diene polymer having an acryloyl group, the unsaturated carboxylic acid compound is acrylic acid and / or a derivative thereof, or the diene polymer is a diene polymer having a methacryloyl group, The golf ball resin composition according to claim 2, wherein the saturated carboxylic acid compound is methacrylic acid and / or a derivative thereof. The polymer is an unsaturated carboxylic acid compound in a reaction product of a diene polymer having a halogenated alkane structure having 1 to 18 carbon atoms at both ends and an unsaturated carboxylic acid compound having 2 to 18 carbon atoms. The golf ball resin composition according to claim 1, which is obtained by neutralizing a carboxyl group derived therefrom. The diene polymer is at least one selected from the group consisting of both ends of a diene polymer and primary to tertiary chloroalkane structures, primary to tertiary bromoalkane structures, and primary to tertiary iodoalkane structures. The golf ball resin composition according to claim 4, wherein and are bonded through at least one selected from the group consisting of an ether bond, a thioether bond, an ester bond, a thioester bond, a silyl ester bond, and a urethane bond. object. The golf ball resin composition according to claim 2, wherein the diene polymer includes a 1,4-cis structure. The golf ball resin composition according to claim 2, wherein the unsaturated carboxylic acid-based compound is at least one selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof. The content of the unsaturated carboxylic acid compound is 8 to 50% by mass, the degree of neutralization of the carboxyl group is 20 to 300%, the content of the unsaturated carboxylic acid compound and the carboxyl group The golf ball resin composition according to any one of claims 2 to 7, wherein the product of the degree of neutralization is 160 to 4500. The polymer is obtained by neutralizing a (anhydrous) dicarboxyl group of a diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more. The resin composition for golf balls according to claim 1. The content ratio of the (anhydrous) dicarboxylic acid is 2 to 30% by mass, the degree of neutralization of the (anhydrous) dicarboxyl group is 20 to 300%, the content ratio of the (anhydrous) dicarboxylic acid, The resin composition for golf balls according to claim 9, wherein the product of the anhydride) and the degree of neutralization of the dicarboxyl group is 80 to 4500. The polymer is obtained by neutralizing a carboxyl group and (anhydrous) dicarboxyl group in a reaction product of a diene polymer grafted with (anhydrous) dicarboxylic acid and a diol compound. The resin composition for golf balls described. The resin composition for a golf ball according to claim 11, wherein the diene polymer includes a 1,4-cis structure. The diol compound has 2 to 20 carbon atoms having 2 hydroxyl groups, 2 hydroxyl groups, 2 to 20 carbon atoms having at least one ether bond, 2 hydroxyl groups, carboxyl The golf ball according to claim 11 or 12, which is at least one selected from the group consisting of a hydrocarbon having 2 to 20 carbon atoms having 1 to 3 groups and a polymer hydrocarbon having 2 hydroxyl groups. Resin composition. The content of carboxyl group and (anhydrous) dicarboxyl group in the reaction product is 4 to 50% by mass, and the degree of neutralization of carboxyl group and (anhydrous) dicarboxyl group in the polymer is 20 to 300%. The resin composition for a golf ball according to any one of claims 11 to 13. The (anhydrous) dicarboxylic acid is at least one selected from the group consisting of (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, and (anhydrous) adipic acid, and the diene polymer. The golf ball resin composition according to claim 9, which is directly bonded to the main chain and / or the terminal. The golf ball resin according to claim 1, wherein the carboxyl group is neutralized with at least one metal ion selected from the group consisting of Na ⁺ , Mg ²⁺ , Ca ²⁺ , and Zn ^2+. Composition. (A) a diene polymer grafted with (anhydrous) dicarboxylic acid and having a 1,4-cis structure content of 41% by mass or more;
(B) a binary copolymer (b-1) of an olefin and an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms, an olefin and an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms Metal ion neutralized product (b-2) of binary copolymer, ternary copolymer of olefin, C3-C8 α, β-unsaturated carboxylic acid and α, β-unsaturated carboxylic acid ester (B-3) and a metal ion neutralized product of a terpolymer of an olefin, an α, β-unsaturated carboxylic acid having 3 to 8 carbon atoms and an α, β-unsaturated carboxylic acid ester (b- 4) A golf ball resin composition comprising at least one selected from the group consisting of 4). The (anhydrous) dicarboxylic acid in the component (A) is at least one selected from the group consisting of (anhydrous) succinic acid, (anhydrous) maleic acid, (anhydrous) glutaric acid, and (anhydrous) adipic acid, and The golf ball resin composition according to claim 17, which is directly bonded to the main chain and / or terminal of the diene polymer. The golf ball resin composition according to claim 17 or 18, wherein the (A) component diene polymer has a content of the (anhydrous) dicarboxylic acid of 1% by mass or more. The golf ball resin composition according to any one of claims 17 to 19, wherein the blending amount of the component (A) is 1 to 70 parts by mass with respect to 100 parts by mass of the component (B). The α, β-unsaturated carboxylic acid in the component (B) is at least one selected from the group consisting of acrylic acid, methacrylic acid, and (anhydrous) maleic acid. Golf ball resin composition. The content of α, β-unsaturated carboxylic acid in the component (B) is 4 to 50% by mass, and the neutralized metal ion in the component (B) has a degree of neutralization of 50 to 500%. The metal ion neutralized product in the component (B) has a product of the content of α, β-unsaturated carboxylic acid and the degree of neutralization of 750 to 5500, according to any one of claims 17 to 21. Golf ball resin composition. The resin composition for a golf ball according to claim 17, further comprising (C) at least one metal ion selected from the group consisting of Na ⁺ , Mg ²⁺ , Ca ²⁺ , and Zn ²⁺ . . A golf ball produced using the golf ball resin composition according to claim 1.